EP0937022B1 - Verfahren zur herstellung von rechtkettigen aldehyden - Google Patents

Verfahren zur herstellung von rechtkettigen aldehyden Download PDF

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EP0937022B1
EP0937022B1 EP97946449A EP97946449A EP0937022B1 EP 0937022 B1 EP0937022 B1 EP 0937022B1 EP 97946449 A EP97946449 A EP 97946449A EP 97946449 A EP97946449 A EP 97946449A EP 0937022 B1 EP0937022 B1 EP 0937022B1
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process according
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alkyl
aryl
group
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EP0937022A1 (de
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Anne Irisa Breikss
Patrick M. Burke
James Michael Garner
Wilson Tam
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Koninklijke DSM NV
EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/1855—Triamide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • the invention relates to a process for the preparation of linear aldehydes by hydroformylation of ethylenically unsaturated organic compounds in the presence of a catalyst system comprising a Group VIII metal and a bidentate organic ligand.
  • the bidentate organic ligand is characterized in that it has two trivalent phosphorus atoms each containing at least one P-C or one P-N bond.
  • a catalyst for such a process is generally a soluble complex of a Group VIII transition metal having a phosphorus containing organic ligand. It is also known that the selection of the catalyst for the hydroformylation reaction has an influence on the rate and selectivity of the product aldehyde(s), but that there is no method for predicting selectivity or reactivity from the structure of a catalytic species.
  • U.S. 5,235,113 teaches a hydroformylation process in which an organic bidentate phosphite ligand containing two phosphorus atoms linked with an organic dihydroxyl bridging group is used with rhodium as a homogeneous hydroformylation catalyst.
  • Aldehydes were produced from ethylenically unsaturated organic compounds, for example 1-octene or dimerized butadiene, using this catalyst system.
  • organophosphorus compounds containing N-bonded pyrrole groups are described in U.S. 3,816,452 and in J. Amer. Chem. Soc. 1995, 117, 7707. However, there has been no teachings of the use of these compounds as ligands for olefin hydroformylation.
  • WO 96/16923 teaches aldehyde preparation by hydroformylation of an ethylenically unsaturated organic compound in the presence of a catalyst system comprising a multidentate phosphorus amide ligand bridged by various groups and a Group 8-10 metal.
  • Grubbs R.H. et al. "Asymmetric hydrogenation by an atropisomeric diphosphinite rhodium complex", Tetrahedron Lett. (22), pp. 1879-80, 1977, disclose a catalyst for use in hydrogenation of ethylenically unsaturated esters and acids.
  • U.S. Patent No. 5,523,453 discloses a catalyst for use in hydrocyanation of monoethylenically unsaturated compounds.
  • This invention provides a process for the preparation of a linear aldehyde, comprising reacting an ethylenically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a catalyst system comprising a Group VIII metal and a ligand of Formula 1, wherein Q is a 2,2'-dihydroxyl-1,1'-binaphthalene or 2,2'-dihydroxyl-1,1'-biphenylene bridging group and R 3 and R 4 are aryl or nitrogen containing heterocyclic groups, for example, pyrrole, indole or imidazole groups bonded to phosphorus through the nitrogen atom.
  • Q shown structurally is:
  • Ligands of the present invention contain two trivalent phosphorus atoms in which each trivalent phosphorus atom is bonded to three organic groups. These ligands may be characterized as phosphinites or phosphorus amide compounds.
  • Phosphinite compounds are characterized in that the trivalent phosphorus atom is linked to the organic group with one P-O bond and two P-C bonds.
  • Phosphorus amide compounds are characterized in that the trivalent phosphorus atom is linked to the organic group with at least one P-N bond and one or two P-O bonds (These compounds are also known as phosphorodiamidites and phosphoramidites, respectively).
  • the ligands of the present invention are bidentate ligands meaning that the two trivalent phosphorus atoms in the molecule are each bonded to the same organic group bridging the trivalent phosphorus atoms together.
  • the aim of this invention is to provide a process for the preparation of linear aldehydes with high catalyst performance (selectivity and/or activity).
  • the process of the present invention achieves a combination of high selectivity towards linear aldehydes and relatively high catalyst activity.
  • linear selectivity is high.
  • the combination of selectivity and reactivity of the present invention is achieved by using a ligand of the following formula in a Group VIII metal-catalyzed hydroformylation process: wherein, Q is a 2,2'-dihydroxyl-1,1'-binapthalene or 2,2'-dihydroxyl-1,1'-biphenylene bridging group.
  • Q is shown structurally as:
  • R 1 and R 2 are independently chosen from the group of hydrogen, alkyl, aryl, triarylsilyl, trialkylsilyl, carboalkoxy, carboaryloxy, aryloxy, alkoxy, alkylcarbonyl, arylcarbonyl, amide, or nitrile.
  • Perferred amide groups are C(O)N(R5)(R7) where R5, R7 are independently C1 to C10 alkyl groups.
  • R 1 and R 2 are preferably a C 2 -C 10 alkyl group, for example ethyl, propyl, isopropyl, butyl, tertbutyl, isobutyl, pentyl, or hexyl.
  • An example of a suitable triarylsilyl group is triphenylsilyl, and examples of suitable trialkylsilyl groups are trimethylsilyl and triethylsilyl.
  • Preferred aryl groups have 6 to 20 carbon atoms, for example phenyl, benzyl, tolyl, naphthyl, anthranyl or phenanthryl.
  • Preferred aryloxy groups have 6 to 12 carbon atoms, for example phenoxy.
  • Preferred alkoxy groups have 1 to 10 carbon atoms, for example methoxy, ethoxy, isopropoxy or tert-butoxy.
  • Preferred alkylcarbonyl groups have 2 to 12 carbon atoms, for example methylcarbonyl, tertbutylcarbonyl.
  • Preferred arylcarbonyl groups have 7 to 13 carbon atoms, for example phenylcarbonyl.
  • R 1 and R 2 are carboalkoxy or carboaryloxy groups, -CO 2 R, in which R is C 1 -C 20 alkyl or C 6 -C 12 aryl.
  • R groups are methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, phenyl, tolyl or naphthyl.
  • 2,2'-dihydroxyl-1,1'-binaphthalene and 2,2'-dihydroxyl-1,1'-biphenylene bridging groups shown in structure 4 can optionally be further substituted with other group on the naphthalene rings.
  • R 3 and R 4 may be the same or different monovalent aryl groups, preferably groups with 6 to 25 carbon atoms.
  • R 3 and R 4 are monovalent aryl groups, for example phenyl, containing at least one group, R 6 , other than hydrogen in a meta- or para-position relative to the phosphorus atom, where R 6 is a electron-withdrawing group as defined by J. March, Advanced Organic Chemistry, second edition, p. 21, McGraw-Hill Book Co. Examples of R 6 are Cl, F, Br, CF 3 .
  • Other preferred groups for R 3 and R 4 are monovalent fused aromatic ring systems with 2 or more rings.
  • R 3 and R 4 are fused aromatic ring systems with 2 or more rings, for example, 1-naphthyl or 7-phenanthryl.
  • R 3 and R 4 may also be the same or different nitrogen containing heterocyclic groups, for example pyrrolyl, indolyl, or imidazolyl groups where the attachment to phosphorus is through a nitrogen atom.
  • ligands in the present invention are:
  • the bidentate phosphinite compounds may be prepared by a variety of methods known in the art.
  • the symmetrical diphosphinites can be prepared as follows. The diarylchlorophosphine is added to a toluene solution of a diol and triethylamine. The reaction mixture is allowed to stir at room temperature, then filtered to remove triethylamine hydrochloride. The product is isolated by removing the solvent under reduced pressure and can be purified by crystallization or chromatography.
  • Unsymmetrical diphosphinites may be prepared in a similar manner.
  • the first diarylchlorophosphine (preferably the more sterically hindered one) is added to a toluene solution of a diol and triethylamine. Once the reaction is complete, the second diarylchlorophosphine is added. Triethylamine hydrochloride is filtered off and the solvent removed under reduced pressure to give the product.
  • the bidentate phosphorus compounds containing P-N bonded pyrrole groups may be prepared at low temperature by reacting phosphorus trichloride with two equivalents of pyrrole in the presence of triethylamine which yields ClP(R 3 ) 2 (where R 3 is N-bonded pyrrole to phosphorus). This intermediate phosphorus chloride compound is further reacted with a diol and triethylamine to give the desired bidentate compound.
  • the indolyl and imidazolyl ligands were prepared in an analogous manner.
  • the catalyst system used in the process according to this invention can be prepared by mixing a suitable Group VIII metal compound with the phosphorus ligand, optionally in a suitable solvent, in accordance with well-known complex-forming methods.
  • the solvent will generally be the solvent used in the hydroformylation.
  • Suitable Group VIII metal compounds are hydrides, halides, organic acid salts, acetylacetonates, inorganic acid salts, oxides, carbonyl compounds and amine compounds of these metals.
  • suitable Group VIII metals are ruthenium, rhodium, and iridium.
  • Group VIII metal compounds are, for example, Ru 3 (CO) 12 , Ru(NO 3 ) 3 , RuCl 3 (Ph 3 P) 3 , Ru(acac) 3 , Ir 4 (CO) 12 , IrSO 4 , RhCl 3 , Rh(NO 3 ) 3 , Rh(OAc) 3 , Rh 2 O 3 , Rh(acac)(CO) 2 , [Rh(OAc)(COD)] 2 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , RhH(CO)(Ph 3 P) 3 .
  • the Group VIII metal is preferably rhodium.
  • suitable ethylenically unsaturated organic compounds are linear terminal olefinic hydrocarbons, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-dodecene; branched terminal olefinic hydrocarbons, for example, isobutene and 2-methyl-1-butene; linear internal olefinic hydrocarbons, for example, cis- and trans-2-butene, cis- and trans-2-hexene, cis- and trans-3-hexene, cis-and trans-2-octene and cis- and trans-3-
  • Suitable olefinic compounds include those substituted with an unsaturated hydrocarbon group including olefinic compounds containing an aromatic substituent such as styrene, ⁇ -methylstyrene and allylbenzene; and diene compounds such as 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene and norbornadiene. It has been found that with the process according to this invention it is possible to prepare 3-pentenal in high yield starting from 1,3-butadiene.
  • the ethylenically unsaturated organic compound can be substituted with one or more functional groups containing a heteroatom, such as oxygen, sulfur, nitrogen, or phosphorus.
  • a heteroatom such as oxygen, sulfur, nitrogen, or phosphorus.
  • these heteroatomsubstituted ethylenically unsaturated organic compounds include vinyl methyl ether, methyl oleate, oleyl alcohol, methyl 2-pentenoate, methyl 3-pentenoate, methyl 4-pentenoate, 3-pentenoic acid, 4-pentenoic acid, 3-pentenenitrile, 4-pentenenitrile, 1,7-octadiene, 7-octen-1-al, acrylonitrile, acrylic acid esters, methyl acrylate, methacrylic acid esters, methyl methacrylate, acrolein and other substituted ethylenically unsaturated compounds.
  • a special class of internally unsaturated organic compounds is 3-pentenenitrile, 3-pentenoic acid and C 1 -C 6 alkyl 3-pentenoate ester compounds.
  • the linear aldehyde compound prepared by this process starting from these compounds can advantageously be used in the preparation of ⁇ -caprolactam or adipic acid, which are precursors for Nylon-6 and Nylon-6,6, respectively.
  • Examples of C 1 -C 6 alkyl 3-pentenoates are methyl, ethyl, propyl, isopropyl, tert-butyl-, pentyl, and cyclohexyl 3-pentenoate.
  • Methyl and ethyl 3-pentenoate esters are preferred because they are more readily available.
  • the 3-pentenenitrile, 3-pentenoic acid and C 1 -C 6 alkyl 3-pentenoate ester compounds may be present in mixtures containing respectively: 2- and 4-pentenenitrile; 2- and 4-pentenoic acid; and C 1 -C 6 alkyl 2- and 4-pentenoate ester compounds. Because these compounds react in a similar fashion as their corresponding 3-isomers to the desired linear aldehyde, the mixture of isomers can be directly used in the process according to the invention.
  • the hydroformylation process according to the invention can be performed as described below.
  • the reaction conditions of the hydroformylation process according to this invention are in general the same as used in a conventional process, described for example in U.S. 4,769,498, and will be dependent on the particular starting ethylenically unsaturated organic compound.
  • the temperature can be from ambient temperature to 200°C, preferably from about 50 to 150°C, and more preferably from 90° to 110°C.
  • the pressure may vary from normal pressure to 20 MPa, preferably from 0.15 to 10 MPa and more preferably from 0.2 to 5 MPa.
  • the pressure is, as a rule, equal to the combined hydrogen and carbon monoxide partial pressure. However, extra inert gases may also be present.
  • the molar ratio of hydrogen : carbon monoxide is generally between 10:1 and 1:10 and preferably between 6:1 and 1:2.
  • the amount of Group VIII metal is not specially limited, but is optionally selected so that favorable results can be obtained with respect to catalyst activity and process economy.
  • the concentration of Group VIII metal in the reaction medium is between 10 and 10,000 ppm and more preferably between 100-1000 ppm, calculated as free metal.
  • the molar ratio of multidentate phosphorus ligand to Group VIII metal is not specially limited, but is optionally selected so that favorable results can be obtained with respect to catalyst activity and desired aldehyde selectivity. This ratio generally is from about 0.5 to 100 and preferably from 1 to 10 (moles ligand/mole metal).
  • the choice of an optional solvent is not critical.
  • the solvent may be the mixture of reactants of the hydroformylation itself, such as the starting unsaturated compound, the aldehyde product and/or by-products.
  • suitable solvents include saturated hydrocarbons (for example, kerosene, mineral oil, or cyclohexane), ethers (for example, diphenyl ether or tetrahydrofuran), ketones (for example, acetone, cyclohexanone), nitriles (for example, acetonitrile, adiponitrile or benzonitrile), aromatics (for example, toluene, benzene, or xylene), esters (for example, methyl valerate, caprolactone), texanol® (Union Carbide), or dimethylformamide.
  • saturated hydrocarbons for example, kerosene, mineral oil, or cyclohexane
  • ethers for example, diphenyl ether or
  • the Grignard reagent of 3,5-bis(trifluoromethyl)bromobenzene in diethyl ether (0.78 moles in ca. 700 mL) was prepared with a literature procedure (Tetrahedron Lett. 1983, 24, 4703-6). With mechanical stirring under nitrogen, this solution was added dropwise to Et 2 NPCl 2 (64.8 gm, 54 mL, 0.37 mol) and dry pyridine (123 gm, 126 mL, 1.56 mol) dissolved in dry diethyl ether (600 mL) while maintaining the reaction solution temperature below 10°C with external cooling. After all the Grignard reagent had been added, the mixture was stirred overnight. While excluding moisture, the magnesium salts were filtered and washed with 500 mL of dry diethyl ether.
  • the hydroformylation was accomplished as follows.
  • a 25 mL glass lined pressure vessel was charged with 5 mL of a solution containing 11.4 gm (100 mmol) methyl 3-pentenoate (M3P), 0.068 gm (0.2 mmol) of dicarbonyl(2,2,6,6-tetramethyl-3,5-heptanedionato) rhodium (Rh(CO)2DPM), 1.34 gm (1.0 mmol) of Ligand 2 and 1.00 gm of tetradecane (internal GC standard) in 100 mL toluene.
  • the molar ratio of ligand to rhodium was 5.
  • the pressure vessel was freed from air by purging first with nitrogen (twice) and then with 1:1 CO/H 2 (twice). The vessel was then pressurized to 75 psi CO and heated to 100°C with agitation for 2 hours. The heat was shut off and the pressure vessel was allowed to cool to room temperature. The excess gases were vented and the products were analyzed by GC.
  • Methyl 3-pentenoate conversion [% methyl 3-pentenoate and methyl 4-pentenoate (M4P) reacted]: 40.0%; linearity [100 x methyl 5-formylvalerate (M5FV) / (methyl 5-formylvalerate + branched formylvalerates)]: 97%, Selectivity (100 x M5FV/A11 products): 64%.
  • First Ligand 4 was prepared as follows.
  • First Ligand 1 was prepared as follows.
  • Ligand 3 was prepared as follows:
  • This example illustrates the hydroformylation of methyl 3-pentenoate with Ligand 2 in a dimethyl adipate solvent at 105°C and 150 psi.
  • Hastelloy-C autoclave was flushed with nitrogen and then with 50 psi of 1:1 CO/H 2 . It was then charged with a solution of 22.8 gm (200 mmole) of methyl 3-pentenoate, 0.53 gm (0.4 mmole) Ligand 2, 0.5 g ortho-dichlorobenzene (ODCB, GC standard), and 16.1 gm of dimethyl adipate solvent. The autoclave was pressured with 1:1 CO/H 2 to 90 psi and heated to 105°C.
  • the reaction was initiated by adding a solution of Rh(CO) 2 DPM (0.068 gm; 0.2 mmole) dissolved in 10 gm of dimethyl adipate.
  • the pressure was immediately adjusted with the CO/H 2 feed gas to 150 psi at 105°C. 1/1 CO/H 2 was continuously fed to the autoclave from a reservoir so as to maintain the total pressure constant at 150 psi. Samples were removed at intervals for GC analysis.
  • the reaction was allowed to run for a total of 21 hours after which it was cooled to 20°C. The excess CO/H 2 was vented through a control valve and the product was discharged.
  • Example Ligand Conversion (%) M5FV Selectivity (%) Aldehyde Linearity (%) 6 7 5.5 37 84 7 8 20 55 83 8 9 6.4 50 80
  • Example 1 The hydroformylation was carried out as described in Example 1 except that methyl 3-pentenoate was replaced by an equivalent amount of 3-pentenenitrile (3PN) and the ligand, temperature, and pressure were varied. Analysis of the products showed a mixture of 3-, 4-, and 5-formylvaleronitriles (FVN) (aldehyde products from pentenenitrile hydroformylation) and valeronitrile (VN; reduction product). The results are summarized in Table 5.
  • the CO/H 2 ratio was 65/35 in this example; the ratio was 50/50 in all other examples; e 247-2B.

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Claims (29)

  1. Verfahren für die Herstellung einer organischen, linearen Aldehyd-Verbindung, ausgehend von einer ethylenisch ungesättigten, organischen Verbindung, durch Hydroformylierung in Gegenwart eines Katalysatorsystems, das ein Metall der Gruppe VIII aufweist sowie einen zweizähnigen organischen Liganden, der zwei dreiwertige Phosphoratome hat, dadurch gekennzeichnet, dass die zwei Phosphoratome mit einer 2,2'-Dihydroxyl-1,1'-binapthalen- oder 2,2'-Dihydroxyl-1,1'-biphenylen-Brückengruppe (Q) verknüpft sind, wobei der Ligand die Struktur hat:
    Figure 00310001
    R3 und R4 sind gleiche oder verschiedene Aryl oder Stickstoff enthaltende heterocyclische Gruppen, wobei der Stickstoff an den Phosphoratomen gebunden ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass Q in der 3,3'-Stellung mit R1 und R2 substituiert ist, wobei R1 und R2 ausgewählt sind aus der Gruppe, bestehend aus H, Alkyl, Aryl, Triarylsilyl, Trialkylsilyl, Carboalkoxy, Carboaryloxy, Aryloxy, Alkoxy, Alkylcarbonyl, Arylcarbonyl, Amide, Halogen und einem Nitril.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass R1 und R2 Carboalkoxyl-Gruppen, CO2R, sind, worin R C1-C20-Alkyl oder C6-C20-Aryl ist.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass R3 und R4 einwertige Aryl-Gruppen sind, die mindestens eine R6-Gruppe außer Wasserstoff in der meta- oder para-Stellung relativ zu dem Phosphoratom enthalten.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass R6 C1-C20-Alkyl, C6-C20-Aryl, F, Cl, Br, CF3 ist.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass R6 CF3, F, oder Cl in einer meta- oder para-Stellung relativ zu dem Phosphoratom ist und R1 und R2 Carboalkoxy-Gruppen entsprechend -CO2R sind, in denen R C1-C8-Alkyl ist.
  7. Verfahren nach Anspruch 1, wobei R3 und R4 wahlweise substituierte Pyrrol-oder Indol-Gruppen sind.
  8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Metall der Gruppe VIII Rhodium ist.
  9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die ethylenisch ungesättigte Verbindung 2 bis 20 Kohlenstoffatome hat.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die ethylenisch ungesättigte, organische Verbindung eine innere ethylenisch ungesättigte Verbindung 4 bis 20 Kohlenstoffatome ist.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die innere ethylenisch ungesättigte Verbindung 3-Pentennitril, 3-Pentensäure oder eine C1-C6-Alkyl-3-pentenoat-Esterverbindung ist.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass die innere ethylenisch ungesättigte Verbindung Methyl-3-pentenoat ist.
  13. Verfahren nach Anspruch 1, bei welchem das Lösemittel ausgewählt ist aus der Gruppe, bestehend aus aromatischen Kohlenwasserstoffen, Ketonen, Aldehyden, Ethern, Estern, Sulfonen und Nitrilen.
  14. Verfahren nach Anspruch 13, bei welchem das Lösemittel das olefinische Ausgangssubstrat und dessen Hydroformylierungsprodukte sind.
  15. Verfahren nach Anspruch 14, bei welchem das Lösemittel der hochsiedende Rückstand ist, der nach der Abtrennung der Hauptprodukte durch Destillation zurückbleibt.
  16. Verfahren nach Anspruch 1, bei welchem das Metall Rhodium mit einer Konzentration von 10 to 5000 Teilen pro Million ist, das Verhältnis Ligand zur Rhodium 0,5 bis 20 beträgt, die Temperatur im Bereich 40°C bis 140°C liegt, der Gesamtdruck im Bereich von 0,1 bis 20 MPa und das CO/H2-Verhältnis 0,1 bis 10 beträgt.
  17. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die ethylenisch ungesättigte, organische Verbindung Butadien ist, das Metall der Gruppe VIII Rhodium ist und R1 und R2 die Carboalkoxy-Gruppen, -CO-OR, sind, in denen R C1-C8-Alkyl ist.
  18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass R3 und R4 Aryl-Gruppen sind, die in mindestens einer meta- oder para-Stellung mit R6 substituiert sind, wobei R6 ausgewählt ist aus der Gruppe, bestehend aus Alkyl, Aryl, CF3, F, oder Cl.
  19. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass R3 und R4 Pyrrolyl-oder Indolyl-Gruppen sind.
  20. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die ethylenisch ungesättigte, organische Verbindung eine innere ethylenisch ungesättigte Verbindung mit 4 bis 20 Kohlenstoffatomen ist, das Metall der Gruppe VIII des Periodensystems Rhodium ist und R1 und R2 Carboalkoxy-Gruppen, -CO2R, sind, worin R C1-C8-Alkyl ist.
  21. Verfahren nach Anspruch 20, dadurch gekennzeichnet, dass R3 und R4 Aryl-Gruppen sind, die in mindestens einer meta- oder para-Stelung mit R6 substituiert sind, wobei R6 ausgewählt ist aus der Gruppe, bestehend aus Alkyl, Aryl, CF3, F, oder Cl.
  22. Verfahren nach Anspruch 20, dadurch gekennzeichnet, dass R3 und R4 Pyrrolyl-oder Indolyl-Gruppen sind.
  23. Zusammensetzung eines Hydroformylierungskatalysators, aufweisend Rhodium und einen zweizähnigen organischen Liganden, die zwei dreiwertige Phosphoratome aufweisen:
    Figure 00330001
    in denen die zwei Phosphoratome verknüpft sind mit einer 2,2'-Dihydroxyl-1,1'-binapthalen-Brückengruppe, (Q), wobei die Brückengruppe Substituenten R1 und R2 in den 3,3'-Stellungen hat, wobei R1 und R2 ein anderer Substituent als Wasserstoff sind, worin R3 und R4 gleiche oder verschiedene einwertige Aryl-Gruppen sind oder worin R3 und R4 gleiche oder verschiedene Stickstoff enthaltende heterocyclische Gruppen sind, wobei der Stickstoff an Phosphor gebunden ist.
  24. Zusammensetzung nach Anspruch 23, dadurch gekennzeichnet, dass Q in der 3,3'-Stellung mit R1 und R2 substituiert ist, wobei R1 und R2 ausgewählt sind aus der Gruppe, bestehend aus H, Alkyl, Aryl, Triarylsilyl, Trialkylsilyl, Carboalkoxy, Carboaryloxy, Aryloxy, Alkoxy, Alkylcarbonyl, Arylcarbonyl, Amid, Halogen und einem Nitril.
  25. Zusammensetzung nach Anspruch 24, dadurch gekennzeichnet, dass R1 und R2 Carboalkoxyl-Gruppen, CO2R, sind, in denen R C1-C20-Alkyl oder C6-C20-Aryl ist.
  26. Zusammensetzung nach Anspruch 23, dadurch gekennzeichnet, dass R3 und R4 einwertige Aryl-Gruppen sind, die außer Wasserstoff mindestens eine R6-Gruppe in der meta- oder para-Stellung relativ zu dem Phosphoratom enthalten.
  27. Zusammensetzung nach Anspruch 26, dadurch gekennzeichnet, dass R6 C1-C20 Alkyl, C6-C20-Aryl, F, Cl, Br, CF3 ist.
  28. Zusammensetzung nach Anspruch 27, dadurch gekennzeichnet, dass R6 CF3, F oder Cl in einer meta- oder para-Stellung relativ zu dem Phosphoratom ist und R1 und R2 Carboalkoxy-Gruppen entsprechend -CO2R sind, worin R C1-C8-Alkyl ist.
  29. Zusammensetzung nach Anspruch 23, worin R3 und R4 wahlweise substituierte Pyrrol- oder Indol-Gruppen sind.
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Families Citing this family (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5886236A (en) * 1997-04-15 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acid salts
MY120454A (en) * 1997-07-29 2005-10-31 Du Pont Improved process of preparation of linear aldehydes
EP1073520B1 (de) * 1998-04-16 2004-06-16 E.I. Du Pont De Nemours And Company Hydrocyanierung von olefinen und isomerisierung von nichtkonjugierten 2-alkyl-3-monoalken- nitrilen
US6229052B1 (en) 1998-05-29 2001-05-08 E. I. Du Pont De Nemours And Company Hydroformylation of olefins using supported bis(phosphorus) ligands
DE19913352A1 (de) 1999-03-24 2000-09-28 Basf Ag Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Phospinamiditliganden
EP1212134A4 (de) 1999-07-21 2003-01-22 Uab Research Foundation Kronige metallether-katalysatoren zur hydroformalition
US6380421B1 (en) 1999-09-20 2002-04-30 E. I. Du Pont De Nemours And Company Multidentate phosphite ligands, catalytic compositions containing such ligands and catalytic processes utilizing such catalytic compositions
US6372939B1 (en) 2000-11-16 2002-04-16 E.I. Du Pont De Nemours And Company Production of 6-aminocaproic acid
US6362354B1 (en) 2000-11-17 2002-03-26 E. I. Du Pont De Nemours And Company Phosphonite ligands, catalyst compositions and hydroformylation process utilizing same
US6437192B1 (en) 2000-11-17 2002-08-20 E. I. Du Pont De Nmeours And Company Hydroformylation of conjugated dienes to alkenals using phosphonite ligands
DE10205702A1 (de) * 2001-02-13 2002-08-29 Basf Ag Verfahren zur Hydroformylierung, Liganden mit von Bisphenol A abgeleiteter Struktur und Katalysator, umfassend einen Komplex dieser Liganden
US7173138B2 (en) * 2001-03-29 2007-02-06 Basf Aktiengesellschaft Ligands for pnicogen chelate complexes with a metal of subgroup VIII and use of the complexes as catalysts for hydroformylation, carbonylation, hydrocyanation or hydrogenation
WO2003018192A2 (de) * 2001-08-24 2003-03-06 Basf Aktiengesellschaft Verfahren zur herstellung von 2-propylheptanol sowie dafür geeignete hydroformylierungskatalysatoren und deren weitere verwendung zur carbonylierung, hydrocyanierung und hydrierung
DE10150286A1 (de) * 2001-10-12 2003-04-17 Basf Ag Phosphinite
MY138064A (en) * 2002-01-24 2009-04-30 Basf Ag Method for the separation of acids from chemical reaction mixtures by means of ionic fluids
DE10205361A1 (de) * 2002-02-08 2003-08-21 Basf Ag Phosphorchelatverbindungen
DE10220801A1 (de) * 2002-05-10 2003-11-20 Oxeno Olefinchemie Gmbh Verfahren zur Rhodium-katalysierten Hydroformylierung von Olefinen unter Reduzierung der Rhodiumverluste
US6664427B1 (en) * 2002-08-29 2003-12-16 E. I. Du Pont De Nemours And Company Process for preparing aldehyde compounds
MXPA05002283A (es) * 2002-08-31 2005-06-08 Oxeno Olefinchemie Gmbh Procedimiento para la hidroformilacion de compuestos olefinicamente insaturados, en particular olefinas, en presencia de esteres de acido carbonico ciclicos.
DE10242636A1 (de) * 2002-09-13 2004-03-18 Basf Ag Verfahren zur Herstellung von Dialdehyden und/oder ethylenisch ungesättigten Monoaldehyden durch Hydroformylierung ethylenisch ungesättigter Verbindungen
DE10313319A1 (de) * 2003-03-25 2004-10-07 Basf Ag Verfahren zur Hydroformylierung
WO2005003070A1 (en) * 2003-07-03 2005-01-13 Lucite International Uk Limited Process for the hydroformylation of ethylenically unsaturated compounds
US7615645B2 (en) 2003-10-21 2009-11-10 Basf Aktiengesellschaft Method for the continuous production of aldehydes
DE10349343A1 (de) * 2003-10-23 2005-06-02 Basf Ag Stabilisierung von Hydroformylierungskatalysatoren auf Basis von Phosphoramiditliganden
GB0403592D0 (en) 2004-02-18 2004-03-24 Lucite Int Uk Ltd A catalyst system
GB0411951D0 (en) * 2004-05-28 2004-06-30 Lucite Int Uk Ltd Carbonylation of ester
KR100547587B1 (ko) 2004-06-12 2006-01-31 주식회사 엘지화학 인을 포함하는 촉매 조성물 및 이를 이용한히드로포르밀화 방법
KR100596365B1 (ko) * 2004-06-12 2006-07-03 주식회사 엘지화학 인을 포함하는 촉매 조성물 및 이를 이용한히드로포르밀화 방법
GB0516556D0 (en) 2005-08-12 2005-09-21 Lucite Int Uk Ltd Improved catalyst system
CA2626107C (en) 2005-11-17 2016-06-21 Lucite International Uk Limited Carbonylation of ethylenically unsaturated compounds
WO2007109549A2 (en) 2006-03-17 2007-09-27 University Of Kansas Tuning product selectivity in catalytic hyroformylation reactions with carbon dioxide expanded liquids
GB0607494D0 (en) 2006-04-13 2006-05-24 Lucite Int Uk Ltd Metal complexes
BRPI0719344B1 (pt) * 2006-12-02 2017-05-02 Lucite Int Uk Ltd ligando bidentado, processo para a carbonilação de compostos etilenicamente insaturados, e, sistema de catalisador
GB0625518D0 (en) * 2006-12-21 2007-01-31 Lucite Int Uk Ltd Carbonylation of conjugated dienes
GB0812297D0 (en) * 2008-07-04 2008-08-13 Lucite Int Uk Ltd Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds
AU2009313838B2 (en) 2008-11-14 2015-02-05 University Of Kansas Polymer-supported transition metal catalyst complexes and methods of use
GB201000078D0 (en) 2010-01-05 2010-02-17 Lucite Int Uk Ltd Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands
CN103402961B (zh) 2010-11-12 2016-03-16 陶氏技术投资有限公司 通过附加水减轻加氢甲酰化方法中的污染
SA112330271B1 (ar) 2011-04-18 2015-02-09 داو تكنولوجى انفستمنتس ال ال سى تخفيف التلوث في عمليات هيدروفورملة عن طريق إضافة الماء
EP2751122B1 (de) 2011-09-30 2018-10-24 Dow Technology Investments LLC Reinigungsprozess
KR102067305B1 (ko) 2012-06-04 2020-01-16 다우 테크놀로지 인베스트먼츠 엘엘씨. 하이드로포밀화 공정
RU2639156C2 (ru) 2012-09-25 2017-12-20 Дау Текнолоджи Инвестментс Ллс Способ стабилизации фосфитного лиганда против деградации
EP2740535A1 (de) * 2012-12-04 2014-06-11 Dow Technology Investments LLC Bidentat-Liganden für die Hydroformylation von Ethylen
CN104837800B (zh) 2012-12-06 2017-08-29 陶氏技术投资有限责任公司 氢甲酰化方法
CN104725170B (zh) 2013-12-19 2019-08-23 陶氏技术投资有限责任公司 加氢甲酰化方法
WO2015094781A1 (en) 2013-12-19 2015-06-25 Dow Technology Investments Llc Hydroformylation process
US10131608B2 (en) 2014-03-31 2018-11-20 Dow Technology Investments Llc Hydroformylation process
CN114072231A (zh) 2019-06-27 2022-02-18 陶氏技术投资有限责任公司 从加氢甲酰化工艺制备溶液以用于贵金属回收的工艺
WO2021126421A1 (en) 2019-12-19 2021-06-24 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms
CN114075241B (zh) * 2020-08-18 2024-02-13 中国石油化工股份有限公司 一种三-1-吡咯基膦配体及其制备方法和应用

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2041776A1 (en) * 1969-05-30 1971-02-05 Inst Francais Du Petrole Novel rhodium contg hydroformylation - catalysts
US3816452A (en) * 1972-01-25 1974-06-11 Du Pont Organophosphorus compounds containing n-bonded pyrrole groups
US4885401A (en) * 1985-09-05 1989-12-05 Union Carbide Corporation Bis-phosphite compounds
US4668651A (en) * 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
US5113022A (en) * 1988-08-05 1992-05-12 Union Carbide Chemicals & Plastics Technology Corporation Ionic phosphites used in homogeneous transition metal catalyzed processes
TW213465B (de) * 1991-06-11 1993-09-21 Mitsubishi Chemicals Co Ltd
US5360938A (en) * 1991-08-21 1994-11-01 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
DE4204808A1 (de) * 1992-02-18 1993-08-19 Basf Ag Verfahren zur herstellung von (omega)-formylalkancarbonsaeureestern
BE1007944A3 (nl) * 1993-12-30 1995-11-21 Dsm Nv Werkwijze voor de bereiding van 5-formylvaleriaanzuur en -ester.
JPH10509973A (ja) * 1994-11-25 1998-09-29 ディーエスエム エヌ．ブイ． アルデヒドの調製法
US5523453A (en) * 1995-03-22 1996-06-04 E. I. Du Pont De Nemours And Company Process for hydrocyanation
TW343195B (en) * 1996-03-15 1998-10-21 Dsm Nv Process to prepare a terminal aldehyde

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